THE POTENTIAL OF WASTE MINE TAILINGS AS GEOPOLYMER

BRICKS FOR CONSTRUCTION MATERIAL IN THE PHILIPPINES

Christian R. Orozco*, Aljon Dimalanta and David Angelo Santos

*Assistant Professor, University of the Philippines Diliman

Diliman Quezon City 1101 NCR Philippines
Email: crorozco@up.edu.ph

Abstract: Mining activities produce waste, called mine tailings, which has toxic components due to the
process it has undergone upon extraction of the mineral from its ore. In the Philippines, large amount
of tailings are being produced every year and if not properly disposed or utilized, it imposes environ-
mental and health risk. One eco-friendly method to utilize mine tailings is converting them into con-
struction materials such as bricks using geopolymerization. The main purpose of the study is to deter-
mine the leaching potential of heavy metals from geopolymerized mine tailings bricks. Results showed
that geopolymerization significantly reduced the leaching of heavy metals from mine tailings. Durabil-
ity test using water absorption also passed the ASTM specifications.

Keywords: Geopolymerization, leaching potential, mine tailings

process, it generates wastes called the mine tail-

1. Introduction
The mining potential of the Philippines is one
of the largest in the world. According to the
Mines and Geosciences Bureau, the country has
nine million hectares or about US $ 1.4 trillion
of mineral reserves (MGB 2010) with gold as
the number one mineral being produced in
terms of value. The Philippines actually ranked
18th in the GFMS Gold Survey List of Top 20
Gold Producing Countries in 2007 (AFRIM
2012). Most small-scale mining in the Philip-
pines is gold mining and 80% of gold produc-
tion in the country comes from these operations.
In 2008 and 2009, the highest portion of gold
produced in the country at 28,198 kg and
26,112 kg are from small scale mines (AFRIM
2012).
There are different methods of extracting gold
from its ore. Some of these methods are Amal-
gamation and Cyanidation. The process of ex-
tracting gold is presented on Figure 1. The pro-
cess involves the use of different concentrations
of various chemicals such as sodium cyanide
(NaCN), carbon, and lime and it also uses
heavy metal like mercury. At the end of the
ings which contain toxic components. Mine
tailings are hazardous to the environment as it
may run off to bodies of water or infiltrate the
soil and contaminate available groundwater.
When this happens, it can lead to human
health risk as the contaminated water may be
drunk by the people around the affected area.
In a study performed by the National Statistical
Commission Board (NSCB), they estimated
that more than 2 million of mine tailings are
produced each year. Since tailings are hazard-
ous due to the process they undergo, measures
in dealing with them should be one. One meas-
ure is to dispose them by impounding on tail-
ings dam, by dry stacking or storing on landfill,
and by using in-pit methods. Another measure
is to utilize them as construction materials since
studies from the past have proven the feasibility
of producing construction materials like bricks
and cement stabilized concrete from mine tail-
ings. However, these measures are unsustaina-
ble as the disposal of large amount of mine tail-
ings will require large area of land and using
cement in stabilizing concrete made of tailings
will mean carbon emissions; hence, the need to

1
seek for a better method of producing construc-
tion materials using mine tailings.
To address the unsustainability in producing
construction materials, an emerging technology
called geopolymerization is proposed. Basi-
cally, geopolymerization is the transformation
of silicate materials, an example is alluminosil-
icate which is a characteristic of mine tailings,
to an amorphous solid by adding an alkaline so-
lution such as aqueous potassium hydroxide or
aqueous sodium hydroxide. (Zhang 2014)
2. Methodology
2.1 Materials
The materials that were used in the research in-
clude small-scale copper mine tailings from
Benguet, alkali reagent grade 98% sodium hy-
droxide NaOH pellets (geopolymer production),
reagent grade 95-97% sulfuric acid (static acid
immersion), reagent grade 69-71% nitric acid,
reagent grade 99.7% glacial acetic acid (TCLP),
and deionized water for general purposes. The
NaOH can be taken from commercially availa-
ble pellets. On the other hand, the sets of equip-
ment used were Instron 5892 series universal
testing machine, TCLP rotary machine, 5-cm
cubic molds, ICP-OES machine, ASTM stand-
ard sieves, mechanical mixer, 2.5-kg weights,
filter papers, glassware, and digital pH meter.
2.2 Preparation of Specimen
In general, the geopolymer brick specimens
were produced by dissolving the aluminosili-
cate compounds in the MT using the alkali base.
To start with, the NaOH solution was prepared
by dissolving the NaOH pellets in deionized
water. It was expected from the chemical reac-
tion that heat will be generated and so it was
allowed to cool down for some time. After-
wards, the NaOH solution was mixed slowly to-
gether with the oven dried MT and was stirred
for about 3-5 mins to ensure homogeneity and
proper dissolution. Different consistencies of
the mixture was observed with varying several
experimental variables such as initial water
content and NaOH/MT ratio.
2.3 Experimental Set-up
Mixing and Molding
2
Before actual production of the geopolymer
paste, a 10 M NaOH solution was prepared by
dissolution of NaOH pellets. After which, the
oven dried MT was crushed to desired fineness
(passing sieve no. 30 or finer). The NaOH solu-
tion was then gradually added and a mechanical
mixer was used for mixing of about 5 mins. Af-
ter mixing, the geopolymer paste was placed in-
side the cubic molds using spatula/hand and
was pressed using 7.5 kg total weights for
around 5 mins.
Curing conditions
The MT used in the mixture were all oven dried
for 24 hours prior to production. After this an-
other 24 hours was given to all molded mixtures
to allow proper setting. The specimens were
then demolded and heat cured in a similar oven
under 60C and 80C for 24 hours.
Aging
The cured brick specimens were then demolded
and allowed to age under ambient temperature
until testing age (i.e. 7-day and 28-day testing
ages to study variation of strength development
over time).
Strength Test
Unconfined Compressive Strength Test (UCS)
ASTM C67-14 Standard Test Method for Sam-
pling Brick and Structural Clay Tile was fol-
lowed to test the compressive strength of the
geopolymer bricks. After aging the specimens
for 7-day and 28-day durations, they were sub-
jected to the universal testing machine Instron
R 5982 with a maximum capacity of 100 kN.
Leaching Potential
The test for leaching potential involves two pro-
cesses. First is the extraction of heavy metals
present in the raw MT and the crushed brick
specimens through the Toxicity Characteristic
Leaching Procedure (TCLP). A rotary equip-
ment, wherein the samples were immersed un-
der an extraction fluid, was used to simulate the
natural environmental conditions. Second is the
quantitative test for the amounts of each heavy
metal that leached out which was done through
Inductively Coupled PlasmaOptical Emis-
sion Spectroscopy (ICP-OES). The standard,
US EPA Test Method 1311 was followed all
throughout the procedure. The heavy metals
checked are: Arsenic, Cadmium, Chromium,
Copper, Lead, and Mercury.

3. Result and Discussion
3.1 Strength Performance
Effect of NaOH/MT ratio
The amount of alkali activator is one of the
most important factors that affect the mechani-
cal properties of geopolymers. Its proportion
with the amount of mine tailings is therefore
necessary in creating a suitable geopolymer
brick. In this study, results of UCS tests
showed a trend that an increase in NaOH/MT
ratio results in lower compressive strengths for
all test cases. This trend is observable in Fig-
ure 1 wherein the linear graphs have negative
slopes. It can also be noted in Table 3 that the
60C curing regime resulted in higher decrease
in strengths than those cured under 80C.
Figure 1. Effect of NaOH/MT Ratio on unconfined compres-
sive strength
The behavior observed indicates that the in-
crease in NaOH activator did not translate into
more dissolved Si and Al species. Furthermore,
even though larger amounts of MT would mean
more source of solid component for the geopol-
ymer matrix, the magnitude of the strengths are
much lower to ASTM standards (see Table 6).
The authors inferred that this might be brought
by incomplete geopolymerization process. Sev-
eral reasons could have been the cause of this
behavior: (1) there is an optimum NaOH/MT
ratio and further increase in alkali activator will
be insignificant; (2) NaOH solution was ab-
sorbed by clay particles resulting to incomplete
dissolution of aluminosilicates; and (3) low
3
compaction effort lowered the rate of reaction
and the voids left permitted the evaporation of
NaOH solution present.
Generally looking at the percentages of de-
crease in strength, it can be inferred that there
are really significant changes in strengths due
to the variation of NaOH/MT ratio. However,
the authors deemed performing statistical anal-
ysis is necessary. The results showed that all
test cases have significant differences in the ob-
served decrease of their strengths and is at-
tributed to variation of the NaOH/MT ratio.
Effect of Curing Temperature
Most literature have reported the significance
of heat treatment as a catalyst for the dissolu-
tion process. In this study, the results of the
UCS test performed showed that in general, in-
creasing the curing temperature from 60C to
80C resulted to a decrease in strength with the
exception of the 0.4, 28-day specimens (as seen
in Figure 5). For the 0.3 ratio, statistical analy-
sis was performed to determine if decrease in
strengths were significant. The results showed
that only the decline in strengths developed
within 7 days was statistically significant. It is
inferred then that the decrease in the 28-day
strengths only resulted from the initial differ-
ence in 7-day strengths.
However, this inference can only be applied
within a range of preparation conditions (e.g.
specified NaOH/MT ratio) since other factors
might take effect. Such example is that too high
temperatures will cause rapid polycondensation
that will hinder further dissolution, rapid evap-
oration and dehydration of the matrix thus re-
sulting in incomplete geopolymerization. These
phenomena explain the decline in strength as
the optimum temperature was probably reached
before 60C or within the 60-80C range. This
inference is further supported by the contrasting
behavior for the 0.4 ratio specimens wherein
the 28-day strength showed a surprising 23%
increase in strength as compared to the ~38%
decrease for the 0.3 ratio specimens. It is then
evident that the 0.3 ratio specimens showed a
more consistent behavior in relation to the cur-
ing temperature and that the 0.4 ratio might be
a transition between one range of optimum tem-
perature to another.
Figure 3. Effect of curing temperature on unconfined com-
pressive strength
Curing Age
The overall trend of the results showed an in-
crease in strength through time (i.e. upon aging)
for all test cases. Similar increasing trends are
seen for the 0.3 ratio specimens as shown by
Table 5. In fact, the highest percentage increase
was observed for 0.3, 60C specimen with 50%
increase as compared to 23% of the 80C coun-
terpart as seen in Table 5. This difference in
strength developments supports the previous
statistical analysis that the decrease in strength
for 0.3 ratio, 28-day specimens was due to the
initial 7-day strength difference and not mainly
due to the variation in temperature. Again sta-
tistical analysis was done and results showed
that the strength did not vary significantly upon
aging. This is contrary to simple comparison
using only the magnitudes of the strengths be-
cause of the 50.8% increase in strength exhib-
ited by the 0.3, 60C specimen. Although the
statistical insignificance of the 7-day and 28-
day strengths might correlate to the general
high early strength development of geopoly-
mers a 50% increase within the studys time pe-
riod is noticeable and thus further investiga-
tions are recommended.
3.2 Leaching Behavior
The graphs of 7-day and 28-day strengths plot-
ted with the raw MT values shows that immo-
bilization of heavy metals is most effective in
lead (~93% decrease in concentration from raw
MT) and copper (~93% decrease from raw). On
the other hand, immobilization of cadmium av-
eraged an 86% reduction from the
4
Figure 3. Effect of age on unconfined compressive
strength.
raw concentration value which is relatively
high considering the low strength values ob-
tained. And in relating it to the U.S. EPA stand-
ard for cadmium this is close to the needed 96%
reduction to fall below the maximum limit. In
general, the concentration results exhibited an
increase in concentration with a decrease in
strength. This can be explained by the correla-
tion between strength development mecha-
nisms and immobilization. The stronger the ge-
opolymer the more likely is that there will be:
(1) more reacted Al and Si species forming into
a stable matrix, and (2) more stable geopolymer
matrices will serve as immobilizing structures.
In contrast, statistical results showed no strong
correlations between the variables and leaching
concentrations. It did however show significant
differences between the raw and the bricks
leached concentrations (i.e. 7-day and 28-day).
The latter indicates an effective immobilization
of the heavy metals in terms of amount. In ad-
dition, there were also no significant de-
crease/increase between the obtained 7-day and
28-day concentrations. To explain this a hy-
pothesis discussed in the full paper, suggested
that since there were no statistically significant
increase/decrease between the 7-day and 28-
day concentrations; the immobilization process
might have been halted prior to the 28th day.
This observation is parallel to the previous in-
significance in the differences between strength
values upon aging.
Figure 4. (Left) 7-day Pb concentrations and (Right) 7-day Cu concentrations with % reduction as compared to US
EPA/R.A. 6969 Limits
4. Conclusion
The results of this study are summarized as fol-
lows:
1. Strength varies inversely proportional
to both NaOH/MT ratio and curing
temperature and proportional to the age,
this is due to premature precipitation of
gels and incomplete geopolymerization.
2. The leaching behavior shows a propor-
tional relationship with strength
3. High rate of reduction ~91% in total
average leaching potential was ob-
served in heavy metal concentrations.
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